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Energy generation performance of a piezoelectric generator depends mainly on several elements such as the structural style, boundary conditions, geometry parameters, materials, vibration-source frequency, and external load. To obtain the optimal energy-harvesting device, the Raleigh method is used to establish the analysis model of circular piezoelectric composite diaphragms. Simply supported and clamped boundary conditions were considered. The relationships between the output power and the structural parameters of piezoelectric composite diaphragms, and the external load resistance and frequency were shown. Given the correlative material parameters and boundary conditions, the output power, using structural parameters, external load, or vibrating frequency as variables, can be calculated. Simulation results show that there are optimal structural parameters and load for a composite diaphragm to achieve the maximum output power. A piezoelectric diaphragm generator with given dimensions tends to achieve higher output power under clamped boundary conditions than that under simply supported boundary conditions.